CN102990080A - Method for preparing carbon nanotube-loaded nano-copper-nickel solid solution by utilizing microwave - Google Patents
Method for preparing carbon nanotube-loaded nano-copper-nickel solid solution by utilizing microwave Download PDFInfo
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- CN102990080A CN102990080A CN2012105164174A CN201210516417A CN102990080A CN 102990080 A CN102990080 A CN 102990080A CN 2012105164174 A CN2012105164174 A CN 2012105164174A CN 201210516417 A CN201210516417 A CN 201210516417A CN 102990080 A CN102990080 A CN 102990080A
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Abstract
The invention provides a method for preparing a carbon nanotube-loaded nano-copper-nickel solid solution by utilizing microwave, relates to the method for preparing the carbon nanotube-loaded nano-copper-nickel solid solution, and aims to solve the problems of complicated process, high cost and difficulty in control of nanoparticle sizes of the preparation method of the existing carbon nanotube-loaded nano-copper-nickel solid solution. The method provided by the invention comprises the following steps of: 1. mixing a NiSO4.6H2O solution with a CuSO4.5H2O solution to obtain a mixing solution A; 2. adding an acidulated carbon nanotube to the solution A to obtain a mixing solution B; 3. mixing a NaOH solution with a hydrazine hydrate solution to obtain a mixing solution C; 4. mixing the mixing solution B with the mixing solution C to obtain a primary extracting solution D after microwave treatment is carried out; and 5. filtering, eluting and drying the primary extracting solution D to obtain the carbon nanotube-loaded nano-copper-nickel solid solution powder. The method can be applied to the technical filed of nanotechnology engineering.
Description
Technical field
The present invention relates to prepare the method for carbon nanotube loaded nanometer copper nickel solid solution.
Background technology
CNT has special structure and good electricity magnetic performance, has received much concern since the self-discovery.Will further improve the physical properties such as its electric conductivity, corrosion resistance, lubricity at the carbon nano tube surface carried metal, can be used as the conductive material of improvement, also can be used as corrosion-resistant, wear-resistant coating, microwave absorbing material etc.Have higher specific area in CNT itself, if metallic particles has higher dispersiveness equally, just so that this composite has very high catalytic activity, may be used on the nanoelectronic instrument, the aspects such as fuel cell and magnetic recording.The preparation method of nano-copper-nickel alloy/carbon nano-tube composite powder exists complex process, cost height and nanoparticle size problem rambunctious at present.Microwave method can make nanometer copper nickel solid solution/carbon nano-tube composite powder under condition simple and easy to control, wherein nanometer copper nickel solid solution size is controlled, is uniformly dispersed.
Summary of the invention:
The present invention is that the preparation method that will solve existing carbon nanotube loaded nanometer copper nickel solid solution exists complex process, cost height and nanoparticle size problem rambunctious, and proposes the method that a kind of microwave prepares carbon nanotube loaded nanometer copper nickel solid solution.
A kind of microwave among the present invention prepares the method for carbon nanotube loaded nanometer copper nickel solid solution to carry out according to the following steps:
One, with the NiSO of 0.05mol/L ~ 0.5mol/L
46H
2The CuSO of O solution and 0.05mol/L ~ 0.5mol/L
45H
2O solution is by volume for 1:(1 ~ 10) ratio mix, ultrasonic processing 1h ~ 2h gets mixed solution A;
Two, the CNT after the acidification is joined solution A, get mixed solution B, ultrasonic 1h ~ 2h, wherein, the CNT quality after the acidification and the ratio of solution A are (1g ~ 3g): 0.1mol.
Three, with the NaOH solution of 0.05mol/L ~ 0.5mol/L and mass percentage content be 85% hydrazine hydrate solution by volume for the ratio of 1:1 mixes, get mixed solution C;
Four, the mixed solution C that the mixed solution B that step 2 is obtained and step 3 obtain is (5 ~ 10) by volume: 1 ratio mixes, then put into micro-wave oven and react 5min ~ 50min, be under 20 ℃ ~ 24 ℃ conditions in temperature, cooling 1h ~ 2h gets just extract D;
Five, the first extract D that step 4 is obtained after filtration, drip washing and dry run obtain carbon nanotube loaded nanometer copper nickel solid-solution powder.
The present invention includes following advantage:
1, the present invention take hydrazine hydrate as reducing agent, produces a large amount of nitrogen when going back native copper, nickel ion under alkali condition, can effectively stop the oxidation of nanometer copper nickel solid solution, and reacted accessory substance is water, does not affect reaction.
2, among the present invention acidified CNT in reaction be dispersant be again template, at tube wall and the mouth of pipe abundant oxy radical is arranged, for nano-copper-nickel alloy provides a large amount of binding sites, simultaneously, it has controlled the size of copper nickel nano particle effectively, and prevents its reunion.
3, the present invention is without surfactant, and can effectively control the size of nanometer copper nickel solid solution, not only electrical property is superior than corronil for the carbon nanotube loaded nanometer copper nickel solid solution of preparation, and overcome the shortcoming that elemental copper is difficult for storing easy oxidation.
4, preparation method's technique of the present invention is simple, and cost is low, and the reaction time is short, and the nanometer copper nickel solid solution pellet is easy to control.
5, the XRD spectra of the composite of the present invention's preparation contains the diffraction maximum of copper and carbon, does not have the diffraction maximum of nickel, but the nickel peak is arranged among the XPS, illustrates that its composite is carbon nanotube loaded nanometer copper nickel solid solution.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one; Fig. 2 is the XRD figure that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one; Fig. 3 is the XPS figure that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
One, with the NiSO of 0.05mol/L ~ 0.5mol/L
46H
2The CuSO of O solution and 0.05mol/L ~ 0.5mol/L
45H
2O solution is by volume for 1:(1 ~ 10) ratio mix, ultrasonic processing 1h ~ 2h gets mixed solution A;
Two, the CNT after the acidification is joined solution A, get mixed solution B, ultrasonic 1h ~ 2h, wherein, the CNT quality after the acidification and the ratio of solution A are (1g ~ 3g): 0.1mol.
Three, with the NaOH solution of 0.05mol/L ~ 0.5mol/L and mass percentage content be 85% hydrazine hydrate solution by volume for the ratio of 1:1 mixes, get mixed solution C;
Four, the mixed solution C that the mixed solution B that step 2 is obtained and step 3 obtain is (5 ~ 10) by volume: 1 ratio mixes, then put into micro-wave oven and react 5min ~ 50min, be under 20 ℃ ~ 24 ℃ conditions in temperature, cooling 1h ~ 2h gets just extract D;
Five, the first extract D that step 4 is obtained after filtration, drip washing and dry run obtain carbon nanotube loaded nanometer copper nickel solid-solution powder.
The present invention includes following advantage:
1, the present invention take hydrazine hydrate as reducing agent, produces a large amount of nitrogen when going back native copper, nickel ion under alkali condition, can effectively stop the oxidation of nanometer copper nickel solid solution, and reacted accessory substance is water, does not affect reaction.
2, among the present invention acidified CNT in reaction be dispersant be again template, at tube wall and the mouth of pipe abundant oxy radical is arranged, for nano-copper-nickel alloy provides a large amount of binding sites, simultaneously, it has controlled the size of copper nickel nano particle effectively, and prevents its reunion.
3, the present invention is without surfactant, and can effectively control the size of nanometer copper nickel solid solution, not only electrical property is superior than corronil for the carbon nanotube loaded nanometer copper nickel solid solution of preparation, and overcome the shortcoming that elemental copper is difficult for storing easy oxidation.
4, preparation method's technique of the present invention is simple, and cost is low, and the reaction time is short, and the nanometer copper nickel solid solution pellet is easy to control.
5, the XRD spectra of the composite of the present invention's preparation contains the diffraction maximum of copper and carbon, does not have the diffraction maximum of nickel, but the nickel peak is arranged among the XPS, illustrates that its composite is carbon nanotube loaded nanometer copper nickel solid solution.
The specific embodiment two: present embodiment and the specific embodiment one are different is with the NiSO of 0.1mol/L ~ 0.3mol/L in the step 1
46H
2The CuSO of O solution and 0.1mol/L ~ 0.4mol/L
45H
2O solution is by volume for 1:(2 ~ 8) ratio mix.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: present embodiment and the specific embodiment one are different is with the NiSO of 0.2mol/L in the step 1
46H
2The CuSO of O solution and 0.25mol/L
45H
2O solution mixes for the ratio of 1:5 by volume.Other step and parameter are identical with the specific embodiment one.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three is that the ratio of the CNT quality after the acidification and solution A in the step 2 is (1.5g ~ 2.5g): 0.1mol.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to three is that the ratio of the CNT quality after the acidification and solution A is 2g:0.1mol in the step 2.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five is in the step 3 to be that 85% hydrazine hydrate solution mixes for the ratio of 1:1 by volume with the NaOH solution of 0.15mol/L ~ 0.35mol/L and mass percentage content.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to five is in the step 3 to be that 85% hydrazine hydrate solution mixes for the ratio of 1:1 by volume with the NaOH solution of 0.25mol/L and mass percentage content.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment eight: present embodiment is different from one of specific embodiment one to seven is that the mixed solution C that the mixed solution B that in the step 4 step 2 obtained and step 3 obtain is (6 ~ 8) by volume: 1 ratio mixes.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment nine: present embodiment is different from one of specific embodiment one to seven is that the mixed solution C that the mixed solution B that in the step 4 step 2 obtained and step 3 obtain mixes for the ratio of 7:1 by volume.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment ten: what present embodiment was different from one of specific embodiment one to nine is to put into micro-wave oven in the step 4 to react 10min ~ 40min, is under 21 ℃ ~ 23 ℃ conditions in temperature, cooling 1.2h ~ 1.8h.Other step and parameter are identical with one of specific embodiment one to nine.
In order to verify beneficial effect of the present invention, carried out following experiment:
Experiment one: a kind of microwave prepares the method for carbon nanotube loaded nanometer copper nickel solid solution to carry out according to the following steps:
One, with the NiSO of 0.2mol/L
46H
2The CuSO of O solution and 0.25mol/L
45H
2O solution is by volume for the ratio of 1:5 mixes, and ultrasonic processing 1.5h gets mixed solution A;
Two, the CNT after the acidification is joined solution A, get mixed solution B, ultrasonic 1.5h, wherein, the CNT quality after the acidification and the ratio of solution A are 2g:0.1mol.
Three, with the NaOH solution of 0.25mol/L and mass percentage content be 85% hydrazine hydrate solution by volume for the ratio of 1:1 mixes, get mixed solution C;
Four, then the mixed solution C that the mixed solution B that step 2 is obtained and step 3 obtain is put into micro-wave oven and is reacted 30min by volume for the ratio of 7:1 mixes, and is under 22 ℃ of conditions in temperature, and cooling 1.5h gets just extract B;
Five, the first extract B that step 4 is obtained after filtration, drip washing and dry run obtain carbon nanotube loaded nanometer copper nickel solid-solution powder.
Fig. 1 is the scanning electron microscope (SEM) photograph that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one, and nanometer copper nickel solid solution is carried on the CNT equably as can be seen from Figure, has effectively controlled the size of copper nickel nano particle, does not reunite.Fig. 2 is the XRD figure that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one; Fig. 3 is the XPS figure that microwave method prepares carbon nanotube loaded nanometer copper nickel solid solution in the experiment one.XRD spectra contains the diffraction maximum of copper and carbon among Fig. 2, does not have the diffraction maximum of nickel, but among Fig. 3 the nickel peak is arranged among the XPS, illustrates that its composite is carbon nanotube loaded nanometer copper nickel solid solution.
Claims (10)
1. a microwave prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that it carries out according to the following steps:
One, with the NiSO of 0.05mol/L ~ 0.5mol/L
46H
2The CuSO of O solution and 0.05mol/L ~ 0.5mol/L
45H
2O solution is by volume for 1:(1 ~ 10) ratio mix, ultrasonic processing 1h ~ 2h gets mixed solution A;
Two, the CNT after the acidification is joined solution A, get mixed solution B, ultrasonic 1h ~ 2h, wherein, the CNT quality after the acidification and the ratio of solution A are (1g ~ 3g): 0.1mol.
Three, with the NaOH solution of 0.05mol/L ~ 0.5mol/L and mass percentage content be 85% hydrazine hydrate solution by volume for the ratio of 1:1 mixes, get mixed solution C;
Four, the mixed solution C that the mixed solution B that step 2 is obtained and step 3 obtain is (5 ~ 10) by volume: 1 ratio mixes, then put into micro-wave oven and react 5min ~ 50min, be under 20 ℃ ~ 24 ℃ conditions in temperature, cooling 1h ~ 2h gets just extract B;
Five, the first extract B that step 4 is obtained after filtration, drip washing and dry run obtain carbon nanotube loaded nanometer copper nickel solid-solution powder.
2. a kind of microwave as claimed in claim 1 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that in the step 1 NiSO with 0.1mol/L ~ 0.3mol/L
46H
2The CuSO of O solution and 0.1mol/L ~ 0.4mol/L
45H
2O solution is by volume for 1:(2 ~ 8) ratio mix.
3. a kind of microwave as claimed in claim 1 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that in the step 1 NiSO with 0.2mol/L
46H
2The CuSO of O solution and 0.25mol/L
45H
2O solution mixes for the ratio of 1:5 by volume.
4. the method for preparing carbon nanotube loaded nanometer copper nickel solid solution such as each described a kind of microwave in the claims 1 to 3, the ratio that it is characterized in that the CNT quality after the acidification and solution A in the step 2 is (1.5g ~ 2.5g): 0.1mol.
5. the method for preparing carbon nanotube loaded nanometer copper nickel solid solution such as each described a kind of microwave in the claims 1 to 3 is characterized in that the ratio of the CNT quality after the acidification and solution A is 2g:0.1mol in the step 2.
6. a kind of microwave as claimed in claim 4 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that in the step 3 with the NaOH solution of 0.15mol/L ~ 0.35mol/L and mass percentage content being that 85% hydrazine hydrate solution mixes for the ratio of 1:1 by volume.
7. a kind of microwave as claimed in claim 4 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that in the step 3 with the NaOH solution of 0.25mol/L and mass percentage content being that 85% hydrazine hydrate solution mixes for the ratio of 1:1 by volume.
8. a kind of microwave as claimed in claim 6 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, and it is characterized in that the mixed solution C that the mixed solution B that in the step 4 step 2 obtained and step 3 obtain is (6 ~ 8) by volume: 1 ratio mixes.
9. a kind of microwave as claimed in claim 6 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, it is characterized in that the mixed solution C that the mixed solution B that in the step 4 step 2 obtained and step 3 obtain mixes for the ratio of 7:1 by volume.
10. a kind of microwave as claimed in claim 8 prepares the method for carbon nanotube loaded nanometer copper nickel solid solution, and it is characterized in that putting in the step 4 micro-wave oven and react 10min ~ 40min, be under 21 ℃ ~ 23 ℃ conditions in temperature, cooling 1.2h ~ 1.8h.
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Cited By (3)
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|---|---|---|---|---|
| CN104592754A (en) * | 2015-01-14 | 2015-05-06 | 黑龙江大学 | Preparation method of polyaniline-coated carbon nanotube-supported copper and nickel solid solution material |
| CN105241936A (en) * | 2015-10-30 | 2016-01-13 | 黑龙江大学 | Method for determination of p-nitrophenol by using carbon nanotube copper nickel solid solution as electrode |
| CN106669680A (en) * | 2016-11-25 | 2017-05-17 | 中国科学院上海高等研究院 | Rod-like nanometer nickel containing metal solid solution catalyst and preparation method thereof |
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| WO2008105820A2 (en) * | 2006-08-25 | 2008-09-04 | Philadelphia Health And Education Corporation | Method of loading a nanotube structure and loaded nanotube structure |
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| CN104592754A (en) * | 2015-01-14 | 2015-05-06 | 黑龙江大学 | Preparation method of polyaniline-coated carbon nanotube-supported copper and nickel solid solution material |
| CN105241936A (en) * | 2015-10-30 | 2016-01-13 | 黑龙江大学 | Method for determination of p-nitrophenol by using carbon nanotube copper nickel solid solution as electrode |
| CN106669680A (en) * | 2016-11-25 | 2017-05-17 | 中国科学院上海高等研究院 | Rod-like nanometer nickel containing metal solid solution catalyst and preparation method thereof |
| CN106669680B (en) * | 2016-11-25 | 2020-08-11 | 中国科学院上海高等研究院 | Rod-shaped nano nickel-containing metal solid solution catalyst and preparation method thereof |
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Inventor after: Zhao Dongyu Inventor after: Wang Qin Inventor after: Han Chunhua Inventor after: Wang Shumin Inventor after: Fu Yue Inventor before: Zhao Dongyu Inventor before: Fu Yue Inventor before: Wang Shumin Inventor before: Wang Qin Inventor before: Han Chunhua |
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Free format text: CORRECT: INVENTOR; FROM: ZHAO DONGYU FU YUE WANG SHUMIN WANG QIN HAN CHUNHUA TO: ZHAO DONGYU WANG QIN HAN CHUNHUA WANG SHUMIN FU YUE |
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